Textile finishing compositions

ABSTRACT

A METHOD OF IMPARTING DURABLE ANTISTATIC FINISH TO HYDROPHOBIC MATERIALS NORMALLY SUSCEPTIBLE TO ACCUMULATING ELECTROSTATIC CHARGES COMPRISING TREATING SAID MATERIALS IN AN ACID ENVIRONMENT WITH A HYDROXY TERMINATED POLYFUNCTIONAL POLYOXYALKYLENE COMPOUND AND AN ACID-CATALYZED NITROGEN-CONTAINING CROSSLINKING AGENT.

United States Patent 3,749,597 TEXTILE FINISHING COMPOSITIONS Earl H. Hartgrove, Jr., Parsippany, N.J., assignor to J. P. Stevens & Co., Inc., New York, N.Y.

No Drawing. Original application Aug. 16, 1968, Ser. No. 753,079, now Patent No. 3,595,813. Divided and this application Mar. 8, 1971, Ser. No. 122,248

Int. Cl. B44d 1/22 US. Cl. 117-138.8 F 5 Claims ABSTRACT OF THE DISCLOSURE A method of imparting durable antistatic finish to hydrophobic materials normally susceptible to accumulating electrostatic charges comprising treating said materials in an acid environment with a hydroxy terminated polyfunctional polyoxyalkylene compound and an acid-catalyzed nitrogen-containing crosslinking agent.

The present application is a division of application Ser. No. 753,079, filed Aug. 16, 1968, now issued as US. Pat. 3,595,813.

This invention relates to novel compositions used to finish hydrophobic substrates and to substrates produced therein.

More particularly, this invention concerns novel compositions used to impart durable antistatic finishes to hydrophobic textile materials which have a tendency to accumulate static charges.

The expression hydrophobic textile materials as used throughout this application refers to synthetic thermoplastics in the form of yarns, slivers, filaments, tows, fibers, articles and garments, and the like produced by drawing, spinning, combing, weaving, knitting or nonwoven procedures. Illustrative hydrophobic textile materials include the preferred polyesters and polyamides, the polyalkylenes such as polyethylene and polypropylene, polyacrylonitrile and the like, as well as the mixtures of one or more of the hydrophobics and/or their blends with natural textiles such as wool and cotton. Rayon for the purposes of this invention is considered to be a natural textile since it is derived from a natural material, cellulose.

Textile materials manufactured from hydrophobic fibers, filaments, yarns, etc., have a relatively low capacity to retain moisture in comparison with their natural counterparts, cotton and wool, and normally tend to accumulate electrostatic charges in their processing during manufacture or during subsequent usage as a textile article or garment. For example, a garment manufactured from untreated hydrophobic materials will cling to the wearer rather than hang smoothly. In order to remove this objectional tendency or reduce it to acceptable levels, a great many antistatic finishes have been developed.

One of the most promising antistatic finishes which has been developed utilizes an alkaline-catalyzed interpolymer of a polyoxyalkylene compound with a polyfunctional amide and a quaternary ammonium salt described in copending Ser. No. 677,090, filed Oct. 23, 1967. This finish provides substantial reduction of the static charge of treated hydrophobic materials as compared to the untreated controls, is compatible with many common textile adjuvants, and is durable to repeated laundering. Unfortunately, the finish causes severe yellowing in white materials and off-shading in colored materials. This yellowing adversely affects the aesthetic appearance of the treated materials and can place the finished materials at a competitive disadvantage compared to the same material before treatment. A comparable finish possessing all of the favorable characteristics of the aforementioned finish which does not cause yellowing would represent a substantial advance in the finishing of hydrophobic materials.

It is therefore an object of this invention among others to provide durable antistatic finishes for hydrophobic materials, particularly polyester and polyamides and their blends with cotton.

Another object is the development of the above antistatic finish which substantially obviates the yellowing and shading problems of previous antistatic finishes.

Yet another object is the production of novel hydrophobic textile materials possessing good hand, durable antistatic properties without comprising the whiteness of undyed materials or the shading of dyed materials.

These objects and many others are attained by treating the hydrophobic substrates with a quantity of a curable antistatic finish, sufiicient upon curing to impart an antistatic finish to the treated substrate, when processed according to the procedure described below.

More specifically, a hydrophobic substrate such as polyester, polyamide or the blends with cellulosics, is treated in acidic environment with:

(a) at least one nitrogen-containing polyfunctional polyoxyalkylene,

(b) at least an acid-catalyzed nitrogen-containing crosslinking compound,

(a) a polyhydroxy-polyglycolamine and (b) at least one acid-catalyzed nitrogen-containing agent,

then dried and cured between about to 200 C. for a suflicient time to form a water-insoluble polymeric film upon the treated substrate and substantially reduce the specific area resistivity of the treated substrate compared to untreated controls.

In order to more easily acquaint the reader with the inventive concept, the following additional description is submitted:

(I) APPLICATION CONDITIONS The treating compositions can be in a variety of forms such as solutions, dispersions, emulsions, suspensions and the like. While aqueous formulations are frequently employed, non-aqueous formulations or mixtures of Water with various solvents can be used. No particular mode of application is required. Any of the application methods used in the textile industry to treat textile articles are satisfactory. These include padding, dipping, spraying, coating among others. The temperature of application is not critical to success and temperatures ranging from room temperature and below up to the boiling point of the solvent system can be employed if desired. The concentration of reagents in the treating solutions can vary con siderably depending upon the wet pickup of the substrate. The critical factor is the add-on gain in the dried substrate. Experience has shown that this add-on must be at least 1%, and usually 3% or more, based upon the dry weight of the substrate to impart a substantial reduction in the tendency of the treated, cured substrate to accumulate electrostatic charges. This quantity of addon is referred to as an antistatic imparting amount of finish. Higher quantities of add-on while affording satisfactory reduction of electrostatic charges give even greater antistatic durability upon laundering, but tend to adversely affect the hand and add to the cost.

( H) CATALYSTS One or more acids or their salts or mixtures of acids and salts serve as satisfactory catalysts for the required catalysis of this invention. Carboxylic acids such as citric acid, and mineral acids such as hydrochloric acid in diluted concentrations can be utilized. Alternatively acidic metallic salts such as zinc nitrate and magnesium chloride can be used by themselves or in conjunction with the acids. No particular quantity of acid need be employed as long as the pH of the system is below 6.0, preferably between about 3.5 and 5.5.

(III) ACID-CATALYZED NITROGEN-CON- TAINING CROSSLINKING AGENTS The acid-catalyzed crosslinking agents employed in this invention are nitrogen-containing resin precursors, particularly those capable of being insolubilized at acid pH values. These resin precursors include those characterized as arninoplast resin precursors, urea-formaldehyde type resins and the substituted cyclic triazines. Suitable groups of resin precursors include dimethylol and polyrnethylol derivatives of urea, ethylene-urea, propylene-urea, dihydroxyethylene-urea, thiourea, dicyandiamide, guanidine, esters of carbamic acid, the methylolated aminotriazines and methylolated triazines as well as their esterification products. The preferred crosslinking agents are 1,3-bis- (hydroxymethyl)-2-imidazolidinone, also known as dimethylolethyleneurea, N ,N ,N tris(hydroxymethyl)- melamine, hexahydro-1,3,5-tris(3 methoxypropionyD-striazine, and mixtures of these agents.

(IV) POLYFUNCTIONAL POLYOXYAL- KYLENE COMPOUNDS The preparations of these compounds are disclosed in US. Patents 3,351,622 and 3,197,463, and have structures selected from the group consisting of and polymers having recurring units selected from the group of consisting of A- is an anion, preferably an anion such as chloride or carboxylate;

m is an integer from 3 to 50, inclusive;

n is an integer from 2 to 4, inclusive;

p is an integer from 2 to 3, inclusive; and

q is an integer from 2 to 20, inclusive.

The preferred polyoxyalkylenes are those characterized within Formulas 4 and 5. The following more specific structures represent the recurring units of polyoxyalkylenes used in this invention:

-N(CHzCH2O) gOH CHz annoomonmon Recurring Unit of PHPA, and

Recurring Unit of PHPA Hydrochloride (V) ANTISTATIC INTERPOLYMERS OF THIS INVENTION As indicated earlier, the antistatic interpolymers of this invention are prepared by exposing admixtures of polyoxyalkylene reactants such as PHPA, acid-catalyzed crosslinking agents such as hexahydro-l,3,5-tris(B-methoxypropionyD-s-triazine, 1,3 bis (hydroxymethyD-Z-imidazolidinone, and N ,N ,N -tris(hydroxymethyDmelamine, and acidic catalysts to elevated temperatures until insolubilization takes place. The following kinds of reactions are'believed to occur during the formation of the insoluble products when PHPA or a suitable salt (as the hydrochloride) is cured with the above crosslinking agents:

(A) A condensation process in which molecules of methanol are eliminated as by-products by reaction between (1) methoxy groups of hexahydro 1,3,5 tris(3- methoxypropionyl)-s-triazine, and

(2) active H atoms on hydroxyl groups of molecules of PHPA or PHPA salt.

As a result, PH-PA (or PHPA salt) is crosslinked and converted into a so-called S-dimensional or ladder" polymer.

(B) A condensation process in which molecules of Water are eliminated as by-products by reaction between (1) hydroxyl groups of l,3-bis(hydroxymethyl)-2- imidazolidinone, and

(2) active H atoms on hydroxyl groups of molecules of PHPA or PHPA salt.

The net result is an insoluble, infusible, nonlinear polymer.

(C) A condensation process in which molecules of water are eliminated as by-products by reaction between (1) hydroxyl groups of N N N -tris(hydroxymethyl)melamin e and (2) active H atoms on hydroxyl groups of molecules of PHPA or PHPA salt.

An insoluble complex polymer results.

(D) In addition to the crosslinking reaction per se, complex polymers are believed to be formed which contain segments of recurring units resulting from self-condensation of resin precursor. That is, PHPA (which may be in neutralized or partially neutralized form) crosslinked by means of l,3-bis(hydroxymethyl)-2-imidaz0lidinone or tris(hydroxyrnethyl)melamine also may contain blocks or grafted segments of recurring units resulting from condensation polymerization of such reactive resin precursors.

(B) When more than one crosslinking reactant is used in the process, the resulting insolubilized product is believed to have crosslinks stemming from each kind of reactant. Furthermore, the resin precursor may be present in the PHPA-containing product as blocks or grafted segments of polycondensed recurring units.

(VI) REACTION CONDITIONS FOR POLYMERIZA- TION AND INSOLUBILIZATION OF THE ANTI- STATIC FINISH In order to obtain the desired antistatic finish and to assure its durability to laundering, he finish must be insolubilized by polymerization in an acid environment. Heating is preferred to accelerate the polymerization reaction. The polymerization reaction is usually carried out in the presence of the hydrophobic substrate by an in situ process. For example, in carrying out the reaction in the presence of a textile substrate, an uncured finish is applied to the substrate to be treated. As indicated earlier, the finish can be in any of several forms. Acidified aqueous solutions are generally preferred for this purpose, although acidification can be done at any time prior to curing. Padding is the preferred form of application. The treated textile substrate is dried preferably between 50 and 105 C. to a moisture content of from about 0.01 to 3.0% by weight moisture, then cured by exposure to elevated temperatures until an insoluble hygroscopic polymer coating is formed.

The temperature at which the polymerization and formation of the insoluble coating takes place can vary considerably according to the reactants, concentrations, pH and catalyst employed. Generally, however, temperatures between about 100-200 C. are preferred.

In order to further describe this invention, the following illustrative examples are submitted. Preceding the examples is a description of the test methods employed in evaluating the finish:

(A) Evaluation test methods Laundering.Each laundering was at 60 C. in a household washing machine with a commercial synthetic detergent. The number of laundering-drying cycles (none, 10, 20, etc.) is indicated by No. L, L, 20L, respectively, in the tables.

Specific area resistivity (SAR).Technical Manual of the American Association of Textile Chemists and Colorists, volume 35, pages 138-139 (1959), Electrical Resistivity of Fabrics, Standard Test Method AATCC 76- 1959. The relative humidity was 30% unless otherwise stated. Fabrics having electrical resistivity values greater than 1 10 ohms are not satisfactorily antistatic, whereas the smaller the value is in comparison with 10 ohms, the more effectively antistatic the fabric is.

Parts and percentages were by weight, unless otherwise noted.

Whiteness (with respect to yellowing), was observed on a subjective comparative basis and rated on a scale of 1 (White) to 25 (severest yellowing, as that resulting from the use of an alkaline catalyst). Whiteness ratings of l to 10 were acceptable, with scores of 1 to 5 being best.

(B) Illustrative examples EXAMPLE 1 Acid-catalyzed antistatic finish for white nylon tricot based on polyhydroxy-polyglycolamine (PHPA) with hexahydro 1,3,5 tris(3 methoxypropionyl)-s-triazine (TMPT) Weighed rectangular portions of white nylon tricot fabric were padded with appropriate aqueous solutions so percentages (on the weight of the fabric) resulted as shown in the following table.

The polyhydroxy polyglycolamine had been synthesized from (1) the alkanolamine having the structure shown in the following equation, and

(2) a polyoxyethylene dichloride having the average composition shown:

Polyhydroxy-polyglycolamine Before PHPA was used in the pad bath, enough 5- normal hydrochloric acid was added to the PHPA to lower the pH to 5, in order to insure compatibility.

In the table, TMPT means hexahydro 1,3,5 tris(3- methoxypropionyl)-s-triazine, and Arquad 12-50 refers to a 50% aqueous solution of dodecyl-trimethyl-ammonium chloride marketed by Armour Industrial Chemical Company.

After the padding step, the treated fabric samples were dried and heated in a forced-draft oven for 3 minutesat approximately C. to bring about formation of an insoluble hygroscopic finish. A whiteness rating was made on each sample prior to washing and also after each sample had been washed in aqueous solution of 0.1% Triton X-100, the trade name of Rohm & Haas Co., for the nonionic wetting agent which is the reaction product of p-(l,1,3,3 tetramethylbutyl) phenol and 9 to 10 mole parts of ethylene oxide, on the average.

The nylon fabric so treated had excellent appearance and durable antistatic properties.

In contrast to the excellent results obtained using an acid-type catalyst (magnesium chloride) with PHPA,

TMPT, and Arquad on nylon tricot, results with respect.

to whiteness were completely unsatisfactory when the acid-type catalyst was replaced by an alkaline one (potassium carbonate). The comparative data are in the accompanying table. (Note: Pretreatment of PHPA by HCl was omitted when the alkaline catalyst was used.)

TABLE FOR EXAMPLE 1 Variation of Example 1 in which a melamine-formaldehyde condensate (Aerotex Resin with TMPT and PHPA A Weighed rectangular portion of white nylon tricot fabric was padded from an aqueous bath so percentages resulted as follows:

PHPA: 6.4% on the weight of the fabric (OW-F) TMPT: 0.5% OWF (abbreviations as in Example 1) MgCl 0.7% OWF M-3: 0.5 OWF (M-3 means Aerotex Resin M-3, a

melamineformaldehyde condensate marketed by American Cyanamid Co.)

As in Example 1, the pH of the PHPA was lowered to 5 before it was added to the pad bath. After padding,

heating for 3 minutes at approximately 150 C. was done as in Example 1. The electrical resistivity was good for a durable antistatic finish, greatly reduced the tendency for electrostatic charges to accumulate on the hydrophobic fabric.

M-3) was used along As in Example 1, nylon fabric having the acid-catalyzed finish'of PHPA and the combination of reactive products based on amino (or arnido) compounds had Nylm tn'cot sample. 10L excellent whiteness. and durable antistatic properties, Example2 2.0mm 0.9x10 14x10 10x10 whereas the alkaline-catalyzed finish was unsatisfactory Untreated control 10 I in those respects. Details are in the accompanying table.

TABLE FOR EXAMPLE 4 Percent on the weight of the fabric Evaluation 1 Aerotex White- Specific area resistivity, ohms White nylon tricot resin Arquad ness Sample No. HPA M-3 DMEU 12-50 Catalyst rating NoL 10L L 30L 6.4. 0.5 0.5 1.2 0.7MgClz 3 23x10" x10 2.8X1O 1.8)(10 6.4 0.5 0.5 0 0.7MgClz 5 215x10 2.5 10 2.4 (10 1.1 10 6.4 0.5 0.5 1.2 0.7 K2003 23 10 10 EXAMPLE 3 EXAMPLE 5 Variation of Example 1 in which 1,3 bis(hydroxyrnethyl) 2 imidazolidinone (DMEU) was used along with TMPT and PHPA Similar to Example 1, with melamine-formaldehyde condensate (Aerotex Resin M-3) and DMEU used in combination with TMPT (along with PHPA, as usual) Weighed rectangular portions of white nylon tricot fabric were padded with appropriate aqueous solutions to yield the add-on percentages shown in the accompanying table. Procedural details resembled those of Example 1, except that a combination of three reactive products based on amino (or amide) compounds had been used instead of just TMPA.

Before PHPA was used in the pad bath, enough S-nor- TABLE FOR EXAMPLE 3 Evaluation Treatment-Percent on the weight of the fabric Specific area resistivity, ohms White- Whlten Ion tricot .Arquad ness Sample hlo. PHPA TMPT DMEU 12-50 MgCh rating No L 10L 20L 30L 10 6.4 0.5 0.5 1.2 0.7 1 1. 3X10 0.7)(10 1.7X10 20x10" 11 6.4 0.5 0.5 0 0.7 9 L2Xl0 1.0)(10 I Not determined.

EXAMPLE 4 mal hydrochloric acid was used to lower the pH of the Similar to Example 1, but with the melamine-formaldehyde condensate (Aerotex Resin M-3) and DMEU used in place of TMPT Weighed rectangular portions of white nylon tricot fab- TABLE FOR EXAMPLE 5 Percent on the weight of the fabric Evaluation Aerotex White- Specific area resistivity, ohms White nylon tricot resin Arquad ness Sample No. PHPA TMPT Xvi-3 DMEU HCHO 12-50 MgC-la ratlng NoL 10L 20L 30L 24-.- 6.4 0.5 0.5 0.5 0 1.2 0.7 2 1.8)(10' 0.4X10 ELEXIO 2.8X10 25.-. 6.4 0.6 0.5 0.5 0.5 1.2 0.7 4 2.0X10 0.8X10 2.5X10 0.7}(10 ric were padded with appropriate aqueous solutions so EXAMPLE 6 percentages resulted as shown in the accompanying table.

Procedural details resembled those of Example 1 (including the comparison test with the alkaline catalyst), except that a combination of melamine-formaldehyde coudensate (Aerotex Resin M-3) and l,3-bis(hydroxymethyl)-2-imidazolidinone (DMEU) replaced TMPA. The padded fabric was heated for 3 minutes at approximately 150 C.

Comparison of various acidic curing catalysts for controlling discoloration on nylon tricot made antistatic by crosslinked PHPA Identified Grams} Ingredient liter 1 Trade name of Procter & Gamble Co. for a complex reactive longchain cationic dispersion formulated as a softener for cellulosics and ny on.

2 Registered trademark of Sandoz, Inc., 61 Van Dam Street, New York, N.Y. 10013, for an optical brightener (a fluorescent white dye).

Aerotex resin M-3 MEU Viva Fibreaetant L Leucophor WSA 2 In order to efiFect drying and curing, each sample was heated at 135 C. for 3 minutes, subjected to high-temperature aging (100 C. for 16 hours) in air. Upon evaluation, all treated fabric samples proved to be durably antistatic. Sample 2, in which phosphoric acid had been used as the acidifying agent, gave the least discoloration and even that very small degree of discoloration was eliminated by washing. Citric acid (Sample 6) resulted in very good whiteness, and hydrochloric acid (Sample 1) re- In order to effect drying and curing, each padded sam ple was heated at 135 C. for 3 minutes. The treated samples and controls were evaluated for antistatic activity after 5 and 15 launderings, respectively, as measured by specific area resistivity.

Whenever potassium carbonate (a base-type catalyst) has been used in the formula added to the nylon, the resulting finish was not nearly so durably antistatic as when magnesium chloride (an acid-type catalyst) was used. This can be seen by the data above in the accompanying table.

EXAMPLE 8 Similar to Example 7, but on 100% polyester taffeta The comparison between acid-type and base-type catalysts demonstrated 'by Example 7 was carried out on a 100% polyester taffeta, a textile based on another chemical class of man-made fiber. Add-on formulas were those tabulated in Example 7. The suffix V identifies the polyester taffeta samples. Drying-curing was effected by heating each padded sample at 135 C. for 3 minutes. As in Example 7, much more durable antistatic activity resulted from the use of acid-catalyzed finishes as compared to base-catalyzed finishes.

TABLE FOR EXAMPLE 8 Polyester sulted in good whiteness. Eut strong acids exert1ng a taffeta Specific area resistivitylohms dehydrating or oxidizing action resulted in discoloration Add-on Formula No. Sample to an undesirable degree (sulfuric acid and nitric acid, from Exampl 15L 20L Samples 3 and 4 respectively). Hence, while various in- -v aaxio g 4.0 i0 10 u a l 1 organic or organic acids may be used in this invention, 5 5133. 1'7X10 strong dehydrating or oxidizing acids are to be avoided. 1.0 10 4.5xi0 7.2Xl0 Among organic acids, those of low volatility are preferred. Connol' Unpadded 10 TABLE FOR EXAMPLE 6 Evaluation-After curing (135 C. for 8 minutes) and aging (100 C. for

hours) S ecifica e ist t White nylon Acid for acidifyp r ares W1 y Ohms tricot sample ing the PHPA Whiteness No L 10L 20L L 1 Hydrochloric.-." Good 0.5X10 25x10" x10 1.4)(10 2 Sulfuric Poor.. 0.4 10 1.4 10 0.9 i0 0.4 10 a Nim do 1.s 10 14x10 1.4Xl0" 1.0 i0 4 oxal c" Fair 0.7 10 1.3Xl0 2.5x10 1.6 10 5 Citric Very good 1.9X109 1.1)(10 1.4)(10 1.9)(10 EXAMPLE 7 EXAMPLE 9 Comparison of acid-type and base-type catalysts as to durability of antistatic finishes for nylon based on crosslinked PHPA Similar to Example 7, but on wool fabric The kind of comparison between acid-type and basetype catalysts demonstrated by Example 9, was carried out on wool fabric which had been dimensionally stabilized through chemical modification by a reactive polymer having terminal aziridine rings. Add-on was as tabulated in Example 7. The suffix W identifies the wool fabric samples. Drying-curing was effected by heating each padded sample at C. for 3 minutes. Again, as

the data in the table indicate, much more durable anti static activity resulted from acid-catalyzed finishes than from base-catalyzed finishes.

TABLE FOR EXAMPLE 7 Add-0n (in percent) based on the weight of the fabric Nylon Specific area resistivity, A d Aerotex trieot1 ohms rqua ICSID. samp e Add-0n formula N0. PHPA TMPT KaCOa 12-50 M-3 DMEU MgClz N0. 5L 15L 71 6. 4 0.8 0. 7 1.2 0 o 0 {ZL gggg gu Z 8 72-T 1:0 10 1.0 10 72 6.4 0 o 1.2 0.6 0.5 ii w w 74 6.4 0.3 0.1 o o o 0 gig:

74-1 6.6 10" 8.0 10 4 -4 o 0 o 0- 2 52 & Control: Unpadded Textmized '1 10 nylon tricot. Untexturized U 10 TABLE FOR EXAMPLE 9 TABLE FOR EXAMPLE 12 Wool Specific area resistivity, Acrylicfabrio ohms woolfab- Specific area resistivity, ohms Add-on Formula No. Sample Add-on Formula N0. rie Sample----- from Example 7 N0. 5L 15L from Example 7 N o. No L 5L 15L 23x10 5 311x10 2.9x10 10 B.9 10 23x10" 3.5 10 5.3mm 27x10 5.1X10 10 4.0x1o 1.4 10 10 GAXIOW 1.0 10 74 7 alxlo 51x10 49x10 43x10 10 Control: Unpadded. 1.5 1o 1.7xm 10 10 EXAMPLE 1O 7 As the above examples and discussion indicate, numsimil t E l 9, b t on t d f b i erous advantages accrue from the practice of this in- Th d f d b t vention. For example, a more durable antistatic finish is 6 Same m o um 1 W companson e wefen ac! provided which does not yellow or adversely affect shadtype base-type catalysts demmstrafed Example 9 15 ing as does the base-catalyzed systems of the prior art. was carnfid out on .100% worsted fabnc Whlcl} been In addition unlike the antistatic finishes which utilize dlmenstonami Stabilized. t h i E the insoluble epoxide crosslinking agents, the systems of a {E PO g g t g gi ffi i this invention employ water-soluble nitrogen-containing z Y t 086 g m s a X crosslinking agents. As a result of this, there is no need 5 5 q e i a g 'g i g g to prepare emulsions or suspensions of variable stability 6 a P eac i 3 2 h or in order to apply the antistatic systems. As a consequence g ii i g s 'g yze a1 5 i 8 Own to of employing nitrogen-containing crosslinking agents, shelf 6 more um e ant e ase'cat yze 5 stability of the formulations is improved, variations in durability are minimized and simpler application and TABLE FOR EXAMPLE formulation techniques can be used.

worsted Numerous changes and modifications can be made in Addqm Formula NO 33 Specific we resistivity, Ohms this invention without departing from the inventive confrom Example? 111 0, p e 1, 1, 1, cept, for example, reactail'ziktls, reaction conlditiorfifs and sugstrates can be varied wi out su stantia y a ecting t e $5831; ilgfiigii $96 1 desired result. The motes and bounds of this invention are aaxlo 10 27x10, Lfixmm 2x101, besvggieigsingitiimfergniisthe claims WhlCh follow.

---------- u 1. A method of imparting durable antistatic finish to hydrophobic materials normally susceptible to accumulat- EXAMPLE 11 ing electrostatic charges comprising treating said materials in an acid environment with: Similar to Example G, but on a blend of polyester (55%) (A) A p 01 yf u n cti O n a p 01y Oxy alkyl e He compound and Wool (45% by Weight) selected from the group consisting of: The comparison between acid-type and base-type cata: 40 (I) (H0CuH2n )zN(CnHhO)mCnHhNECHHHOHM lysts illustrated by Example 7 was carried out on a fabnc made from a blend of polyester (55%) and wool by weight). Add-on was as tabulated in Example 7. The (Hocnmn Q 2A suflix Y identifies the polyester-wool fabric samples. Dry- H H ing-curing was effected by heating each padded sample 45 (3) at 135 C. for 3 minutes. Data again indicated that more [(HOCnH2n )3N( 11 21: )m n Zn n Zn )3]' durable antistatic activity resulted from acid-catalyzed finishes than from basgcatalyzed film-311% and polymers having recurring units selected from the group consisting of:

TABLE FOR EXAMPLE 11 5 H G H n 211 m n 221- Pol st wooi er fi wonn n on' Fabric Specific area resistivity, ohms Add-on Formula N0. Sample irom Example 7 No. No L 5L 30L and 215x10 1.1 10 10 8.0x10 6.8X10 3.2 10 74 i' ii ifi 58 in (5) Control: Unpadded 418210 215E10 1il 11 2n )m n 2n C H2 (0O H2n)q H 60 EXAMPLE 12 wherein Similar to Example 7, but on a blend of Orlon (70%) A- is an anion;

and wool (30% by weight) In is an integer from 3 to 50, inclusive; Durability comparisons between acid-type and basen or 4; t g p1s20r 3; and

ype catalysts were carried out on a fabric made from t f t 20 1 d a blend of Orlon acrylic fiber and wool 30% by (B) i j jfz gg g gi weight) as described in Example 7. [Orion is a registered ing agentrselecteg from g p consisgfing of 1 3 :Z of 3 g i g S$2 bis (hydroxyrnethyl)-2-imidazolidinone, hexahydro- 'f was as In ,Xamp e f 70 1,3,5-tris(3-methoxypropionyl)-s-triazine; melamineidentifies the acrylicwool fabric samples. Drying-curing formaldehyde condensates and their mixtures, t was effected by heating each padded sample at 135 C- then subsequently exposing said treated material to elefQT 3 mlmltes- Once more i durablllty of the acid vated temperatures until an insoluble film is formed and catalyzed systems w re superior 120 3 86 f t basea durable finish is produced, said insoluble film being catalyzed systems. present in an antistatic imparting amount.

2. The method of claim 1 wherein the polyfunctional polyoxyalkylene is of the structure:

-r cHzoH2o)1zoH2on,

U3}I6(OCH:CH3)QOH wherein A- is an anion selected from the group consisting of chloride and carboxylate.

3. A method of imparting a durable antistatic finish to hydrophobic textile materials selected from polyester, polyamide, and their blends with cotton comprising:

(A) Treating each one hundred parts by weight of textile material to be finished, in an acid environment with (1) liquid carrier containing from 3 to parts by weight polyhydroxy-polyglycolamine having recurring units of the formula:

\+ N(CH;CHzO)1z 2 2 aHa(OCH CH OH wherein A- is an anion, and

(2) from 0.3 to 10 parts by weight of at least two liquid-carried orosslinking agents selected from the group consisting of 1,3-bis(hydroxymethyl)-2 imidazolidinone, hexahydro-1,3,5- tris(3-methoxypropionyl)-3-triazine and melamine-formaldehyde condensates,

(B) Drying the treated textile material between about 50 C. and 105 C., and

14 (C) Heating the dried and treated material between about C. and about 200 C. until an insoluble polymer is formed and a durable antistatic finish is imparted therein. 4. The process of claim 3 wherein the liquid carrier contains water.

5. The process of claim 3 wherein the liquid carrier is substantially free from water.

References Cited UNITED STATES PATENTS 3,258,358 6/1966 Cohen 117-139.5 A 3,008,215 11/1961 Pitts 117139.5 A 3,134,686 5/1964 Baechtold 117139.5 A 3,420,703 1/1969 Kirkschnek et a1. 117139.5 2,846,337 8/1958 Cooke et a1 26029.4 3,021,232 2/1962 Pretka 2602 3,351,622 11/1967 Tesoro 117138.8 A 3,353,993 -11/l967 Kida et a1. 260-29.4 3,356,524 12/1967 Buell 260-29.4

FOREIGN PATENTS 976,712 12/ 1964 Great Britain 260849 WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US. Cl. X.R.

8--1|15.5, 115.6, 115.7; 117-138.8 E, 138.8 N, 138.8 VA, 139.5 A, 143 A 

